It is not a relief valve but an integral safety device for the prevention of over pressure situations.
When a trigger gun is released there is a short pressure spike that causes the springs in the unloader to reduce pressure on the pump head. In doing so the spring releases pressure on the head and allows water to bypass, usually in a short loop to allow the pump to continue pumping for a short time only. As the loop is very short the water will heat up quite quickly due to friction from pumping and eventually cause a seal failure leading to oil in the crankcase and a potentially expensive repair.
As it is a primary safety device it is set at the factory for the specifications of the pump and should never be adjusted. There are springs and o-rings that wear so adjustment will accelerate the wear.
Pumps are all positive displacement. By that I mean that depending on pump RPM it will put out the same amount of water every time. All the tip does is put a restriction in the end of the system that provides the pressure; just like putting your thumb over the end of a garden hose. Tips are sized according to the orifice number. Check out
http://www.arnorthamerica.com/spraynozzlechart.html
for an excellent one. It is simple to use, find the closest flow to the rating of your pump in the body. The left hand column is the number size of the tip and the top row is the pressure that size orifice will create. NEVER, EVER over pressure your machine. Extreme damage will result. Tips are designed to work most effectively at 6-12" from the surface to be cleaned. A 0 tip will give you concentrated force and is highly dangerous and should only be used with great care. 15 and 25 degree tips are most common as they strike a balance between coverage and power. A 40 degree tip is best used for rinsing as the power disipates rapidly. You can also adjust the pressure by moving the tip away from the work. FYI, typically a coin-op car wash will use 1200 PSI and a 40 degree tip to use as a comparison.
There are also two basic types of unloaders: hard and soft.
Hard unloaders trap pressure in the line so the hose is fairly stiff and can be difficult to drag around. They are cost effective and tend to be more durable and forgiving.
Soft unloaders allow for a soft hose because they relieve trapped pressure. They are usually more expensive and tend not to be as durable.
Personal preferences dictate which one you use.
Simply put, adjust pressure by changing tips. Never adjust the unloader as it is a primary safety device.
Hope this helps? Cheers.